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PericyclicReactionsElectrocyclizations,Cycloadditionsand
SigmatropicRearrangements
FromICTWiki

Organicreactionsmaychieflybecategorizedinto3broadclasses,namely,i)ionicreactions,ii)radicalreactionsandiii)pericyclic
reactions.Althoughavastmajorityofreactionsinorganicchemistryaretypicallyionic,theothertwocategoriesofreactions,thatis,
radicalreactionsandpericyclicreactions,haveassumedimportanceoftheirown.Theyarevirtuallyindispensableinthesynthesisof
organiccompoundsingeneral.

Thechemistryofreactionsmediatedbyionicandradicalintermediateswasreasonablywellunderstoodby1960s.However,asizeable
numberofreactionsthatpresentedmechanisticcuriosityweredocumentedbythen.Thesereactionswereintriguingandnotreadily
explicable.Itwasin1965thatWoodwardandHoffmannjointlyrecognizedadifferentbasisforthesereactions.Theirpathbreaking
collaborativeeffortledtotheadvancementofsocalledconservationoforbitalsymmetryasabasisforexplainingoccurrenceand
nonoccurrenceofcertainreactionswithagivenmodeofenergizationandstereochemistryassociatedwiththeproducts.

Concertedreactionsarethoseinwhichthebondbreakingandbondmakingoccursimultaneouslyalthoughnottothesame
magnitude.Pericyclicreactionsaredefinedasconcertedreactionsthatproceedviacyclictransitionstates.Ingoingfromreactant/sto
theproduct/s,thesymmetryoforbitalsinvolvedinthebondbreakingandbondmakingwereconsideredtobestrictlyconserved.This
conservationoforbitalsymmetrywasshowntopermitpredictabilityastotherelativereactivityandregioaswellasstereoselectivity
intheproducts.Thetransitionstatesinvolvingcontinuouselectronicreorganizationwithcertainorbitalorientationsarefavored
energetically,whileothersleadtohighenergytransitionstates.

Ingeneral,thepericyclicreactionscanbeassociatedwithfollowingattributes:

Theyoccurinasinglestep,andarethusfirstorderreactionsofcourse,theyarecharacterizedbytheabsenceoftheinvolvementof
anyreactiveintermediateduringthecourseofthereaction.

Thebondbreakingandmakingoccursimultaneously,althoughnotnecessarilytothesamedegree.

Theyexhibithigh(sometimeseventotal)stereospecificityandstereoselectivity.

Theconfigurationoftheproductformeddependson:

configurationofthereactants
numberofelectronpairsundergoingredistribution
reactionconditions(suchasthermalorphotochemical)

Therateisunaffectedbyfactorslike:

solventpolarity(exceptifthereactantsarecharged,e.g.,1,3dipolarcycloadditions)
thepresenceofradicalinitiators/inhibitorsorcatalysts(exceptwhendealingwithsomeacidcatalyzedDielsAlderreactions)

Theyoccurthermallyorphotochemically

Allthepericyclicreactionsabidebytheprincipleofmicroscopicreversibility.

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Basedonidentificationofcertaincommonfeatures,WoodwardandHoffmannclassifiedpericyclicreactionsintofollowing5basic
types:

Table1summarizesoverallchangesthataccompanythedifferentclassesofpericyclicreactionsdescribedaboveintermsofelectronic
organization.

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Theoccurrenceofanyofthesepericyclicreactionswithaparticularmodeofenergizationandthestereochemicalconsequencecanbe
rationalizedusingorbitalsymmetryconsiderations.Indeed,thepericyclicreactionsassumespecialimportancefromthepointofview
successfulcollaborativeeffortbetweentwogreaticons(R.B.WoodwardandRoaldHoffmann)ofexperimentalandtheoretical
chemistry,whichhasledtowidespreadacceptanceofmolecularorbitaltheoryasappliedtoorganicreactions.

Inordertoexplainthecourseandthehighregioandstereospecificityofpericyclicreactions,threedifferentmodelswithdifferent
degreesofsophisticationcanbeemployed:

Itwasthefirsttheorytoexplaintheoutcomeofseveralpericyclicreactions.Themethodisbasedontheprincipleoforbitalsymmetry
conservationthroughoutthereaction.

Conservationoforbitalsymmetryrequiresthatthetransformationofmolecularorbitalsofreactantsintothoseofproductsproceed
continuouslybyfollowingareactionpathalongwhichthesymmetryoftheseorbitalsremainsunchanged.

Theorbitalsymmetryconsiderationshavebeenshowntoaccountforthousandsofcomplexreactionoutcomesinavery
straightforwardwaywithoutrequiringanycomplexmathematicalcalculations.Thekeytounderstandingthemechanismsofthe
concertedpericyclicreactionswastherecognitionbyWoodwardandHoffmannthatthepathwayofsuchreactionsisdeterminedby
thesymmetrypropertiesoftheorbitalsthataredirectlyinvolved.

Itismucheasiertousethantheoriginalorbitalsymmetryarguments.Thismethoddoesawaywithallorbitalsofthereactants,but
takesintoconsiderationofonlytheinteractionsbetweenHOMOandLUMO.

Itistheeasiesttoapplyforallreactiontypes,butitisnotaseasytounderstandwhyitisvalid.Themethodisbasedontheprincipleof
aromaticstabilizationofthetransitionstateTSaccordingtoHckelsMOtheory.

Beforegoinganyfurther,letuslookatthemolecularorbitalsofconjugatedpolyenicsystemsandtheirrelativeenergies.Asthe
conjugationincreases,thedifferenceintheenergybetweentheHOMOandLUMOdecreases.

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Anelectrocyclicringclosureinvolvescreationofanewbondattheexpenseoftwoterminalporbitalsofaconjugatedsystem
witharesultantreorganizationoftheconjugatedsystem.Electrocyclicringformationandringopeningaredenotedbythenumberof
electronsinvolved.Forexample,inthecyclizationof1,3butadienetocyclobutene,fourelectronsaretransformedintooneand
onebond.Accordingly,thisreactionisclassifiedas4nelectrocyclicreactionwithn=1.Inthecyclizationof1,3,5hexatrieneto
cyclohexadiene,overall6electronsareinvolved,sothatitisreferredtoas4n+2electrocyclization(withn=1).

Thefollowingarefewprototypeexamplesofelectrocyclicreactionsofneutralpolyenes.

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Electrocyclicreactionsarenotlimitedtoneutralconjugatedpolyenes,butarealsoapplicabletoionicconjugatedsystemsasillustrated
belowforsomeexamples:

Duringringopeningorclosing,thestereochemistrymaychangedependinguponthenatureofringclosingoropening.Thering
openingorclosingcanoccurvia2ways.Itissaidtobeconrotatary,ifmotionofthetwoarrows,whichdetermineeitherring
openingorringclosing,isinthesamedirection(clockwiseoranticlockwise).Inotherwords,onespeaksofconrotatoryopeningor
closure,iftheorbitalstiltinthesamedirectioninsuchamannerthattheiroverlapleadstoringopeningorclosing.Inthesame
manner,onespeaksofdisrotatoryopeningorclosure,iftwoarrowsortheorbitalsmoveintheoppositedirectionforafavorable
overlapleadingtotheringopeningorclosing.Conrotatoryringopeningleadstoatransitionstatethatischaracterizedbyatwofold
axisofsymmetry,whiledisrotatoryringopeningleadstothetransitionstatecharacterizedbyplaneofsymmetry.

Now,letuslookatthestereochemicalconsequencesassociatedwithringopening:

Intheaboveexample,theproductmaybeformedbyclockwiserotationofbothMesubstituentsofthecyclobutene.Ofcourse,there
occursequalprobabilityforconrotatoryringopeninginwhichboththesubstituentsmoveanticlockwise.Foreverydisrotatoryor
conrotatoryringopeningorringclosing,therearetwopathwayspossible.Thesizeofthesubstituents/groupsandtheelectronicnature
oftheresultantproductdictatewhichoftwopathwaysismorefavorable.

Itwasobservedthat1,3butadienesundergoconrotatoryanddisrotatoryclosureunderthermalandphotochemicalconditions,
respectively.Incontrast,1,3,5hexatrieneswerefoundtoundergoclosureinanoppositemannerundersimilarconditionsasshown
below.

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Furthermore,achangeinthereactionconditionsinvolvingthermaltophotochemicalmodeofenergizationwasnotedtoleadtoa
reversalinthestereochemistryasshownbelow.

Thedependenceofthestereochemicaloutcomeoftheproductsonthereactionconditions,i.e.,thermalandphotochemical,canbebest
explainedbasedontheconservationoforbitalsymmetrydevelopedbyWoodwardandHoffmann.

TheWoodwardHoffmannrulesweredevelopedtoexplaintheobservedstereospecificityofelectrocyclicringopeningandring
closingreactionsattheterminiofopenchainconjugatedpolyeneseitherbyapplicationofheat(thermalconditions)orapplicationof
light(photochemicalconditions).

AccordingtoWoodwardandHoffmann,thedevelopingoverlapbetweenthetwoterminalporbitalscanhaveconstructivebonding
interactionsonlyifthelatterareinphase.Inordertoaccomplishbonding,theterminalporbitalscanrotateinthesame(conrotation)
oroppositedirections(disrotation)asshownbelow:

Fordevelopmentofnewbondinginteractionsinthetransitionstate,theterminimustmoveinconrotatoryanddisrotatoryfashionin
4and6electronsystems,respectively,asshownbelow.

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Thecrucialinsightsemergedinrelatingthethreeparameters,viz.,(i)thesenseofrotation,(ii)thenumberof4electronsinvolved
(n),and(iii)thesymmetriesofthehighestoccupiedmolecularorbitals(HOMOs).

Now,letuslookatthesymmetryobservedfortheHOMOsofsomeopenchainconjugatedsystems.Aparticularmolecularorbitalcan
havetwopossiblesymmetryelementsatwofoldaxisofsymmetry(C2)and/oramirrorplaneofsymmetry().

Thesesimpleobservationsprovedremarkablypowerfulintherationalizationofalargenumberofexperimentalfindingsand
establishingqualitativepredictionsconcerningreactivity.

Letusconsidertheelectrocyclicringclosureof1,3butadiene.Thereactioninthisinstancemayproceedviaeitherconrotatoryor
disrotatorypathway.Intheconrotatorymode,thetransitionstateisassociatedwithaC2axisofsymmetry,whilemirrorsymmetryis
associatedwiththeTSinthedisrotatorymode.

Themolecularorbitalsofthereactantsandproductsarecorrelatedintermsofbeingsymmetricorantisymmetricwithregardtothea
particularsymmetryelement.ApplyingthesymmetryelementonaMOshouldgiverisetosameMO.Insuchacase,theMOissaidto
besymmetricforthatsymmetryelement.IfthesymmetryoperationleadstoadifferentMO,thentheMOissaidtobeantisymmetric.
Forexample,2of1,3butadieneissymmetricwithrespectto180rotationabouttheC2axisandantisymmetricwithrespectto
reflectioninthemirrorplane().

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Similarly,theMOsofcyclobutenecanbesaidtobesymmetricorantisymmetricwithrespecttosymmetryelementsC2and.The
tablebelowconsolidatesthesymmetryelementsassociatedwiththeMOsofcyclobutene:

WoodwardrealizedthatthesymmetryelementsofallorbitalsuntiltheHOMOwerepreservedintheMOsoftheproduct.Thus,the
symmetryoftheTSalsomustlikewisebeconserved.Ifasymmetryelementispresentthroughoutthecourseofthereaction,viz.,in
thereactant,transitionstateandproduct,thenitisconsideredasaconservedsymmetryelement.Similarly,antisymmetryissaidtobe
conserved,ifitismaintainedthroughoutthecourseofthereaction,thatis,inthereactant,transitionstateandtheproduct.For
instance,intheHOMOofa4conjugatedsystem,C2axisofsymmetryisconservedinreactant,TSandproductasshownbelow:

Amolecularorbitalcorrelationdiagramconnectsthemolecularorbitalsofreactantandproductbasedontheconservationof
symmetry.Frommolecularorbitalcorrelationdiagrams,theelectronicstatediagramscanbederivedthatcorrelatetheelectronic
states,viz.,groundstateandtheexcitedstate,ofthereactantandtheproduct.Thisallowsthepredictionoftheenergiesassociated
withtheTSbarriersviacorrelationdiagrams.Thelattercannowbeconstructedbysimplydrawingthemolecularorbitalenergy
diagramsofbothreactantandproductsidebysideandthencorrelatingthesymmetryelementsassociatedwiththeirorbitals.

Letusfirstconsidertheelectrocyclizationof1,3butadienetocyclobutene.Themolecularorbitalsaredrawnintheirincreasingorder
ofenergyandthesymmetryofeachMOanalyzed.LetusexaminetheC2symmetryoftheMOsofreactant(1,3butadiene)and
product(cyclobutene).The1MOofbutadieneandMOofcyclobuteneareantisymmetric(A)withrespecttoC2axisofsymmetry
andthereforearesaidtobecorrelatedwitheachother.Likewise,2andMOsaresymmetric(S)withregardtoC2axisandare
connectedbydottedlines.Inasimilarmanner,alltheMOsofreactantcanbecorrelatedwiththeMOsoftheproductsbasedontheC2
axisofsymmetry.Underthermalconditions,thefourelectronsofthereactantareaccommodatedintheorbitals1and2thelatter
canberepresentedas correspondingtoanoverallsymmetryrepresentedasA2S2.Similarly,thetwoandelectronsof
productcyclobutenearefilledintheandMOs.Thelattercanberepresentedas22withanoverallsymmetryofS2A2.Upon
conversionof1,3butadienetocyclobutene,theorbitalsymmetryofthesystemisconserved.Toputitinsimplewords,itmeansthat
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theconversionof2(HOMOofreactant)intoMO(HOMOofproduct)isthermallyallowed.Now,sincethebondformation
requiresthetwoterminalporbitalstooverlapinphase,thecyclizationmustoccurinconrotatoryfashion.Hence,theconjugated
substrateshaving4electronsundergoconrotatoryringclosurethermally.

Now,letusexaminethecorrelationdiagramforphotochemicalringclosureof1,3butadiene.Inthiscase,oneoftheelectronsin
reactantisexcitedfrom2to3.Asaresult,theelectronsinreactantarenowfilledinthreeorbitals1,2and3whichare
representedas theoverallsymmetrycorrespondstoS2A1S1.ThelattermatcheswithS2S1A1theoverallsymmetryof
productMOs,namely,,and*correspondingto21*1.Thebondisformedbytheoverlapoftheterminalporbitalsof2.This
ispossiblebydisrotatoryclosurewhichleadstobondinginteractionsbetweenthetwoporbitalsunderconsideration.Thus,the
disrotatoryclosureof4conjugatedsubstratesoccursphotochemicallyascanbeunderstoodfromthefigureshownbelow.

Thecorrelationdiagramsfor6systemscanalsobeconstructedlikewise.Suchdiagramsenabledeductionofrulesconcerningring
closure/openingbyaparticulartypeofmotionoftheorbitals,i.e.,disrotatoryorconrotatory,undergivenexperimentalconditions,
namelythermalorphotochemical.TheselectionrulesthusgeneralizedbyWoodwardandHoffmannforelectrocyclicreactionsare
showninthetablebelow.

In1952,KenichiFukuiscameupwithanovelmoleculartheoryforunderstandingthereactivityinaromatichydrocarbons.Despitea
lotofcriticismtohiswork,FukuiwentontosharetheNobelPrizeinChemistrywithHoffmannfordevelopingasimplisticapproach

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tounderstandthereactionmechanisms.Fukui'sownworkrevolvesaroundtheanalysisoftheinteractionsbetweenthefrontier
molecularorbitals(FMOs),namely,HOMO,LUMOandSOMO.

Accordingtohiswork,thereactivitycouldbegaugedbysimplylookingatthefrontiermolecularorbitals(HOMO/LUMO).Weknow
thattheinteractionoftwoMOsofleadstotwonewMOs,namely,bonding(lowerenergy)andantibonding(higherenergy).Incases
wherebothinteractingMOsarefilledwithelectrons,bondingbetweentwocannotoccursincethebondinginteractionsarenullifiedby
theantibondingones.However,iftheoneoftheMOsfilledandthatoftheotherisemptyorpartiallyfilled,thenthetwoMOsattract
eachotherandundergobonding.Basedonsuchobservations,FukuisuggestedthattheoutcomeofinteractionsbetweentheFMOscan
bepredictedfromthenatureofthelatter.VariousinteractionsbetweentheFMOs,theirnatureandtheoutcomearetabulatedbelow.

FukuiusedtheseinteractionstodevelopabetterunderstandingoftheconclusionsdrawnfromWoodwardHoffmannrules.Unlike
WoodwardHoffmannsapproach,theFukuistheoryconsidersonlyfrontiermolecularorbitals(FMOs).Thus,theFMOtheory
simplifiesreactivityintointeractionsbetweenHOMOofonespeciesandLUMOoftheother.

Thestereochemicaloutcomeofelectrocyclicringclosureofthe1,3butadienecanbeeasilyunderstoodusingthisformulation.Under
thermalconditions,2istheHOMOfor1,3butadiene.Forconstructivebondinginteractionstooccur,theterminalporbitalsmust
rotateinconrotatorymannertoyieldtheproductcyclobutene.Whileonphotoirradiation,oneelectronispromotedfrom2to3.As
aresult,underphotochemicalconditions,3becomestheFMO.Thecyclizationofbutadienetocyclobutenenowinvolvesdisrotatory
closureofthetwoterminalporbitalsthatgivesrisetoinphasebondinginteractionsasshownbelow.Furthermore,forsubstituted
butadienessuchastrans,trans2,4hexadiene,samereactantformstransandcisdimethylcyclobuteneexclusivelyunderthermaland
photochemicalconditions,respectively.Thisvariationinthestereochemistrycanbeattributedtodifferenceinthemodesofrotation,
namelydistortionandconrotation,inthetworeactions.

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Letusnowexaminetheelectrocyclicringclosureof1,3,5hexatrieneasubstratewith(4+2)electrons.Underthermalconditions,
3istheHOMOforthehexatrienylskeleton.IntheTS,thetwoterminalporbitalsundergodisrotatoryclosuretofacilitatethein
phasebondinginteractions.Conversely,thephotochemicalreactioninvolvesexcitationofoneelectronfrom3to4.Sincethetwo
terminalporbitalsin4areoutofphase,theringclosureoccursinaconrotatoryfashionleadingtobondinginteractionsinthe
productcyclohexadiene.Forsubstitutedopenchainsubstratessuchastrans,cis,trans2,4,6octatriene,conrotationleadstoformation
ofthecorrespondingcisdiastereomer,whiletransdiastereomerisformedbydisrotation.

Letusnowlookatthefollowingexample.

Inathermalreaction,conrotatoryringopeningofbicycliccyclobutenecontainingcisfusedmethylenechain1leadstocycliccis
transdiene.Followingtableshowsthetemperatureforaseriesofcompounds1withincreasingnatwhichthehalflifeisabout2
h.

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Thehalflivesindicatethestabilityofthecompounds.Fromthedataitisobservedthatforlargernvalues,i.e.,forlargerringsystems
thestabilityofcompound2increases.Again,forringsystemsuntiln=3/4,stabilityofcompound1increaseswithincreasing
temperature.Thisisunderstandablefromtheconsiderationofreliefofringstrain.Transolefinbecomesincreasinglystrainedasthe
ringsizedecreases.Thatiswhyforlargerringsystems,thecompound2becomesincreasinglystable.

Letusconsiderthefollowingsolvolysisreaction.

TheexperimentallyobtainedproductformationofthesolvolysisreactioncanbeexplainedbyinvokingthecleavageofCClbond
withconcerteddisrotatoryringopeningofthecyclopropanering,whichcanbeunderstoodbythefollowingtwoobservations:

ThisratedifferencecanbebestexplainedbytheconsideringsimultaneousdisrotatoryringopeningandCObondcleavage.The
cyclopropaneringopeningshouldoccurinsuchawaythatthereisabondinginteractioninthetransitionstateamongsttheorbitalsof
carbonsthatareinvolvedinbondbreaking.

Here,weareconsideringHOMOoftheCCbondandLUMOoftheCOTsbond.Inthefirstcase,twomethylgroupsbeingclose
enoughinterferewitheachotherstericallyresultinginmoreincreaseintheenergyofthetransitionstateascomparedtothesecond
onewheretwomethylgroupsdonotinterferewitheachother.Thus,thesecondcompoundundergoessolvolysisreactionmuchfaster
thanthefirstone.

Intheexampleshownbelow,twoepimersgivedifferentsolvolysisproducts.Ineachcase,lossofendohalogenatomstakesplace.
Thisisduetothefactthatonlythelossofendohalogenatomcanbeassistedbytherequireddisrotatoryopeningofcyclopropanering.
Thisfactcanbesubstantiatedbythefollowingexamples:

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Compound2undergoessolvolysisreadilyat125C,whileitsepimer1isrecoveredunchangedafterprolongedtreatmentwithacetic
acidat210Cduetounavailabilityofendohalogenatom.

Weknowthatforeachmodeofrotation(conrotatoryanddisrotatory),therearetwopathwayspossible.Thesetwopathwaysmaylead
todifferentproducts.Letusconsiderthefollowingexamples.

[[File:TR...png|center]

Againforthefollowingreactant,wecanhavetwopossibleproducts:

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Thisspecificwayofconrotatoryringopeningcannotbeexplainedsolelybystericfactors.Weshouldexpectthermodynamicallymore
stabletransolefin1basthemajorproduct.Fromtheseexamples,itisobviousthatdonorsubstituentinvariablyisturnedoutward
andtheacceptorsubstituentinvariablyisturnedinward.Thistypeofselectivityiscalledtorquoselectivity.

Themechanisticrationaleforthistorquoselectivityisthestereoelectronicfactor.

Theinwardrotationresultsinafavorableorbitalinteractionbetweentheacceptingorbitalandtheporbitalsoftheterminalcarbon
atomsoftheconjugatedsystem.Thislowerstheenergyofactivation.Thisisthereasonforthepreferenceofinwardrotationinthe
presenceofacceptorsubstituents.Inthecaseofdonorsubstituents,theinwardrotationwouldresultinelectrostaticrepulsion
betweentheelectronrichorbitalsandthusleadstoapreferentialoutwardrotation.

Itistheelectrocyclicreactionofpentadienylcation,whichundergoes4conrotatoryringclosure.

Intheexampleshownabove,acrossconjugateddienoneformsacyclopentanonewhentreatedwithacidinthiscase,aLewisacid
suchasFeCl3isemployed.TherelativestereochemistryofhydrogensatC1andC5atomsistrans,asrequiredbytheconrotatory
cyclization.Intheabsenceofsilylgroup,thedeprotonationinthelaststepoccursmainlyfromC1resultinginthelossof
stereochemicalinformationatthatcentre.Aninterestingfeatureofthisreactionisthatthereactionis5endotrigatbothends,

whichisforbiddenbyBaldwinsrule.

Example1

Example2

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Example3

cisStilbenecanbeconvertedtophenanthrenebyaprocesswhichinvolvesphotochemicalconrotatoryringclosingreactionfollowed
byoxidation.

Example4

Example5

Example6

Example7

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Example8

PreparationofDewarBenzene:

Example9

Example10

Example11

Cycloadditionisaprocessinwhichtwoormoreunsaturated(conjugated)molecularsystemsreacttoformaringbytransformingthe
electronsofbondsintonewbonds.Inotherwords,itistheunionoftwoindependentsystemsinamannerthatacyclicsystem
results.Thenewbondsarecreatedattheexpenseofbonds.Intramolecularcycloadditionsarealsopossibleincaseswherethe
moleculecontainstwoindependentunsaturatedmoieties.

Cycloreversionissimplyreverseofcycloaddition.Sincecycloadditionsinvolvetwoormoreunsaturatedbondsofasamemoleculeor
twodifferentmoleculesleadingtoacyclicadduct,thereisanetreductioninthebondmultiplicity.

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Cycloadditionreactionsaredepictedtoas[m+n]additions,whereinthecycloadductisformedbetweentwosystemsofmandn
electronsofcourse,themoleculecontainsmorethan2electrons,itoughttobeconjugated.Severalcombinationsofmolecular
systemsarepossibleforcycloadditionreactions,someofthemareshownbelow:

Theformationofbondsbetweenthereactingcomponentsmayoccurintwodifferentways.Whenthecycloadditionoccursinsucha
waythatthenewbondsareformedonthesamefaceofthesystem,themodeofadditionissaidtobesuprafacial,moresimply
supra.Inthesamemanner,ifthenewbondsareformedontheoppositesidesofthesystem,themodeofadditionissaidtobe
antarafacial,moresimplyantara.

Accordingly,cyclizationoftwocomponentscanoccurinthreedifferentcombinationsofthetwomodesofaddition:

Herethetworeactantsapproacheachotherfromthesameface.Thetwosigmabondsareformedonthe
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samefaceofeachthetwosystems.

Thecycloadditionoccursinsuchamannerthatthenewbondsareformedonthesamefaceforoneofthe
twocomponents,whiletheyareformedontheoppositefacesforthesecondcomponent(seebelow).

Theoppositefacesofthetwomoietiesinteractwitheachotherduringthiscycloaddition.Thetwosigma
bondsareformedontheoppositefacesofthetwosystems.

Theorbitalcorrelationdiagramsforcycloadditionreactionscanbedrawnasdiscussedforelectrocyclicreactions.Thecorrelation
diagramstrackwhichorbitalsofthereactantstransformintowhichorbitalsoftheproductsalongthereactioncoordinate.Toconstruct
thecorrelationdiagramsforcycloadditions,certainruleshavebeenputforwardbyWoodwardandHoffmann,whichareasfollows:

1.Definegeometryfortheproposedinteraction.

2.DrawMOsofthereactantsandtheproductsintheorderofincreasingenergy.

3.DefineeachMOasbeingeithersymmetricorantisymmetricwithrespecttothesymmetryelementsfoundinthestructuresofthe
startingmaterial,products,andtransitionsstates.

4.PopulatetheMOswithelectrons,beginningwiththegroundstateMO.

5.CorrelatereactantMOswiththoseoftheproductMOsoflikesymmetry.IfallthebondingMOsofthereactantcorrelatewith
bondingMOsoftheproduct,thereactionissaidtobeallowed.IfabondingMOinthereactantbecomesanantibondingMOinthe
product,thereactionthenissaidtobeforbidden.

[2+2]Cycloadditionisthesimplestcase,andletsconsideritsoccurrenceunderthermalconditionstobeginwith.Thereare4possible
waysinwhichthetwocomponentsmayinprinciplereacttogivethecycloadduct.Theyare:[2s+2s],[2a+2s],[2s+2a],
[2a+2a].However,thegeometricconstraintsprecludeanyantarafacialadditionbetweenthetwocomponents,therebylimitingthe
approachofthetwocomponentstosuprafacialmode.Letsanalyzethesymmetryelementspresentinthemolecularorbitalsofthetwo
reactants:

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Asshownabove,onemayidentifytwomirrorplanesofsymmetry.Takingthisintoconsideration,wecannowdrawthecorrelation
diagramforthermal[2+2]cycloadditionoftwoethylenemoleculesasshownbelow.

Accordingtotheprincipleofconservationoforbitalssymmetry,forthermalcycloadditionoftwoethylenemoleculestoform
cyclobutane,thetwoorbitals(1and2)correspondingtothetworeactingethylenemoleculesmustbecome1and2*orbitalsin
theproduct.Inotherwords,thetwoorbitalsofthereactantsaresymmetryrelatedtothe1and2*orbitalsintheproduct.Inorder
toconservetheorbitalsymmetry,theproductisformedintheexcitedstate.Itisthusobviousthatsuchatransformationinvolvesvery
highenergybarrier.Infacttheenergyrequiredtomovetwoelectronsfrom1to3*orbitalrequiresanenergyof~115kcal/mol,and
thustheprocessmaybesaidtobeforbidden.

Letuslookatthephotochemical[2+2]cycloaddition.Inthiscase,oneelectronispromotedfrom2to3*orbital,asaresultofwhich
theorbitalpicturebecomescompletelydifferent.Now,the1,2and3*orbitalsofthereactantsarerelatedbysymmetryto1,2
and3*orbitalsofthecyclizedproduct.Asaresult,theenergybarrierisdrasticallyreducedandthereactionnowbecomesallowed
withtheformationofproductintheexcitedstate.Therefore,[2+2]cycloadditioncanbesaidtobephotochemicallyallowed.

Someexamplesofphotochemical[2+2]cycloadditionsaregivenbelow:

Example1

Example2

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Example3

Example4

Example5

Example6(Intramolecular)

Example7(Intramolecular)

Thisreactionisofsignificance,asgenerally2+2cycloadditionusingN=Nisverydifficult.

Example8(Intramolecular)

Intheaboveexample,thephotochemicalenergyisusedtocreatemoleculeswithhighstrainenergycontent.

Example9

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Here,dependingonwhatR*is,thestrainenergyinthequadricyclaneproductcanbeashighas2030kcal/mol.Thiskindofreactions
canpotentiallybeexploitedforlightharvestingandconvertingphotochemicalenergyintostrainenergy,whichmaybereleasedas
thermalenergyundercatalyticringopeningconditions.

Example10

Example11

Example12

Regioselectivityincycloadditionsreferstopreferentialformationofoneproductovertheotherpossibleoneasaconsequenceof
favorableorientationofthereactantsduringbondbreakingandbondmaking.Incycloadditions,thegenerallyobserved
regioselectivityisguidedbyelectroniceffect(bothinductiveandresonance)asshownbelow.

However,inductiveandresonanceeffectsdonotalwaysexplaintheregioselectivitiesofcycloadditionreactions.Onesuchexampleis
shownbelow.Theproductthatisexpectedbasedoninductiveeffectaloneisnotformedregioselectively.

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ThereasonfortheseeminganomalycanbereconciledwhenweconsidertheorbitalpictureandvisualizetheHOMOLUMOofthe
reactants.

Thus,foreffectivematchingoftheorbitalcoefficients,theinteractionbetweenorbitalsmustoccurasshownabovetoaccountforthe
regioselectivityofthisphotochemicalreaction.

Asdiscussedbefore,thethermal[2+2]cycloadditionviasuprasupraadditionofthereactantsisnotpossible,sincetheinteraction
betweenHOMOandLUMOofthereactingpartnersisbondingatoneendandantibondingattheotherasshownbelow.

However,therearetwosituationsinwhichthesupraantaraadditionisfavoredthermally.Thesearewhen:

A.oneofthereactantscontainsonesphybridizedcarbon,and

B.theolefinissignificantlytwisted.

Thermal[2+2]cycloadditionreactionsbecomefeasiblewhenoneofthereactantsisanelectrophilicalkenethatcontainsasp
hybridizedcarbonasapartofthedoublebond,suchasketeneandisocyanate.Thelattermayapproachthealkeneorthogonallyin
suchawaythattheHOMOofoneandtheLUMOoftheotherdevelopbondinginteractions.Ingeneral,whenthereactingpartners

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approacheachotherinanorthogonalorientation,thebondinginteractionsareoffsetbytheantibondingrepulsionsfromtheotherside
oftheorthogonallyapproachingpartnertoprecludethermalcycloaddition.However,whenoneofthereactantisaketeneor
isocyanate,thecentralsphybridizedcarbonofferstheincentivetostabilizethetransitionstateandpermitcycloaddition.Ascanbe
seeninthefollowingfigure,theextraporbitalmayfacilitateextrabondinginteractions.

Example1

Example2

Example3

Example4

Example5

Example6

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Thesecondscenariowhenthe[2+2]cycloadditionoccursinasupraantarafashioniswhenthereactingalkenesaretwisted
significantly.Thetwistingthusenablesfavorableoverlapofthebondingorbitals,whilediminishingrepulsiveinteractions.Asshown
below,thesupraantaraadditioninorthogonalorientationleadstostereoinversionatoneofthecarbons.Thus,thermal[2+2]
cycloadditionisassociatedwithstereoinversionatoneofthecenters.Incidentally,therearenotmanyexamplesknownforthiskindof
cycloaddition.

Example1

Example2

Inthecaseofcycloadditionsinvolving6electronssuchas[4+2]cycloaddition(DielsAlder)reactions,thermalreactionsarefoundto
beallowed.Letuslookatthecorrelationdiagram,seebelow,tounderstandthereasonbehindthis.Ascanbeseen,theorbital
symmetryisconservedthroughoutthecourseofthereactionforallfilledbondingmolecularorbitalsingoingfromreactanttothe
product.Thethermal[4+2]cycloadditionreactionsthushavenosymmetryimposedrestrictions.Underphotochemicalconditions,one
oftheelectronsfrom2isexcitedto3.Thismakesthissuprafacialreactionsymmetryforbidden.

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Fukuiobservedthatinabimolecularreaction,thetransitionstatecanbeconsideredasperturbationofthereactants.Thisapproachled
totheformulationoftwoconclusions:

Fukuishowedthatthemostsignificantterminthesecondorderperturbationtreatmentwhenappliedtoabimolecular
reactionistheonethatcorrespondstotheinteractionofthefilledorbitalsofonecomponentwiththeemptyorbitalsoftheother.

Themagnitudeofinteractiondependsontheenergyassociatedwiththeseorbitals.Accordingly,thedegreeofinteractionis
converselyrelatedtothedifferenceintheenergiesofHOMOandLUMO.

ThesecondruleclearlyemphasizeswhytheHOMOLUMOinteractionsaresolucrativeinexplainingtheoutcomeofbi(andeven
multi)molecularpericyclicreactionsbetweenreactantsthatarehighlysymmetric.

Now,letusexaminethethermal[2+2]and[4+2]cycloadditionsbasedonFMOtheory.In[2+2]cycloaddition,theHOMOofoneof
thecomponentshastheorbitalphasessimilar,whiletheLUMOofthesecondcomponenthastheorbitalswithoppositephases.Thus,
thebondingandantibondinginteractionsbetweentheorbitalsofthetwocomponentsforbidthecycloadditionfromoccurring
thermally.Ontheotherhand,theterminalorbitalsintheHOMOofthe4dienicsystemhaveoppositephases,andsoaretheorbitals
ofLUMOofthe2system.Thus,forcycloaddition,theorbitalsareinphaseattheterminileadingtobondinginteractions.The[4+2]
cycloadditionisthusathermallyallowedprocess.

Incontrast,for[2+2]photochemicalcycloaddition,theorbitalsattheterminiforbothofthe2systemsareinphase,whichmakesthe
reactionallowed.For[4+2]photocycloadditions,theterminalorbitalsinthe4conjugatedsystemareoutofphasewiththoseofthe
2system.Asaresult,thereisnoconstructivebondingpossibleandthereactionissaidtobephotochemicallyforbidden.

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Wemaynowconsolidatetheselectionrulesforcycloadditionreactionsdependingonnumberofpelectroninvolvedinthetransition
stateasshownbelow.

Intermsofthestereoselectivity,letusconsiderthereactionbetweenmaleicanhydrideandcyclopentadiene.TheFMOtheory
beautifullyexplainsastowhytheendoproductisfavoredovertheexoproduct.Thedienophile,i.e.,maleicanhydride,iselectron
deficient,andcontributesLUMO,whiletheHOMOiscontributedbycyclopentadiene.Despitethegreaterthermodynamicstabilityof
theexoproduct,theendoproductiskineticallyfavoredandisthemajorproductofthereaction.Ascanbeseeninthefollowing
figure,theTSleadingtoendoproductgetsenergeticallyloweredduetotheoperationofthesecondary(nonbonding)orbital
interactions.

Example1

Example2

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Example3

Example4

Example5

Example6

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Example7

Example8

Thealkenebond,anallylicCHbondandanolefincanparticipateinapericyclicreactioninwhichthedoublebondshiftswith
concomitantformationofnewCHandCCbonds.TheallylicsystemreactssimilartothedieneinaDielsAlderreaction,whilein
thiscasetheotherpartneriscalledenophile,analogoustothedienophileintheDielsAlderreaction.TheAlderenereactionrequires
hightemperaturesforoccurrenceofthereactionbecauseofthehigheractivationenergyandstereoelectronicfactorsassociatedwith
breakingoftheallylicCHbond.

FollowingistheorbitalpicturethatenablesunderstandingofthefeasibilityofAlderenereactionbasedonFMOtheory.

Example1

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Example2

Example3

Example4:ConiaReaction

Example5:Carbonylenereaction

Dipolesarespeciesthatarezwitterionicinnaturewithafilledoctet.Ingeneral,theyare4electronsystems.

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TheHuisgencycloadditionisareactionbetweenadipolarophileanda1,3dipolarcompoundthatleadsto5membered(hetero)cyclic
system.Examplesofdipolarophilesincludealkenes,alkynes,carbonyls,nitriles,etc.1,3Dipolarcompoundscontainoneormore
heteroatom/sandcanbedescribedashavingatleastonemesomericstructurethatrepresentsthechargeddipole.

1.

2.

3.

1.

2.

Nitrileoxidethusreactswithdipolarophiletogeneratehydroxycarbonylcompounds.

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